CN101423829A - Adding calcium fly ash micropore glass carrier for immobilized enzyme and preparation method thereof - Google Patents
Adding calcium fly ash micropore glass carrier for immobilized enzyme and preparation method thereof Download PDFInfo
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- CN101423829A CN101423829A CNA2008101607779A CN200810160777A CN101423829A CN 101423829 A CN101423829 A CN 101423829A CN A2008101607779 A CNA2008101607779 A CN A2008101607779A CN 200810160777 A CN200810160777 A CN 200810160777A CN 101423829 A CN101423829 A CN 101423829A
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- fly ash
- polyurethane foam
- adding calcium
- calcium fly
- titanium dioxide
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- Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
Abstract
The invention relates to a calcium-enhanced fly ash porous glass carrier of an immobilized enzyme and a method for preparing the same, which belongs to the technical field of microorganism. The method comprises the following steps: selecting a polyurethane foam material the porosity of which is between 70 and 85 percent; placing the polyurethane foam material in a sodium hydroxide solution the concentration of which is between 10 and 20 percent; soaking the polyurethane foam material at a temperature of between 40 and 60 DEG C for 1 to 3 hours; repeatedly rubbing and rinsing the polyurethane foam material with clean water to remove the alkali solution, and drying the polyurethane foam material naturally; according to weight percentage, preparing 55 to 75 percent of calcium-enhanced fly ash, 2.5 to 10.5 percent of binder, and 10 to 25 percent of water into slurry; adding 5 to 20 percent of nanometer titanium dioxide powder into the slurry; dipping the slurry in dry polyurethane foam to repeat for a few times, and drying the slurry at a temperature of between 100 and 200 DEG C for at least 12 hours to obtain a porous glass blank containing the nanometer titanium dioxide; keeping the temperature when the porous glass blank is heated up to a glass sintering temperature of between 1,200 and 1,400 DEG C for 60 to 90 minutes; and performing furnace cooling to obtain the porous glass carrier with highly communicated vents.
Description
Technical field
The present invention relates to microbial technology field, specifically a kind of porous glass matrix material that utilizes that adding calcium fly ash is made for main raw material, being used for fixing enzyme and preparation method thereof.
Background technology
We know, at present, sintered glass is as the inorganic carrier of immobilized enzyme, the physisorphtions that adopt more, be about to that enzyme is adsorbed onto on the porous glass matrix and the method that makes enzyme immobilization, but this immobilized enzyme and carrier interactions a little less than, the enzyme that is adsorbed comes off from carrier easily, loading capacity is generally very low, has easily to make some enzyme that the absorption sex change takes place often.Also there is the people once to make carrier, adopts the covalent attachment legal system to be equipped with immobilized enzyme with sintered glass, but this immobilized enzyme operation more complicated, reaction is fierce, and reaction conditions is wayward, often causes the decline even the complete deactivation of enzyme activity in preparation process.
Summary of the invention
Technical problem to be solved by this invention is in order to overcome above-mentioned the deficiencies in the prior art, provides that a kind of immobilized enzyme is effective, immobilized enzyme vigor height, production cost industrial residue adding calcium fly ash low, that can make full use of power plant be the porous glass matrix material that main raw material is made.
The technical scheme that the present invention solves the problems of the technologies described above employing is: adopting adding calcium fly ash, binding agent, water, nanometer titanium dioxide titanium valve is that feedstock production forms, and its technical characterictic is that the weight of raw material consists of and contains: adding calcium fly ash 55～75%, binding agent 2～11%, water 10～25%, nanometer titanium dioxide titanium valve or nanometer titanium dioxide zirconium powder 5～20%.
The weight of adding calcium fly ash ingredient of the present invention requires: calcium oxide 20～31%, aluminium sesquioxide 9～16%, silicon-dioxide 42～53%, ferric oxide 1～3%, manganese oxide 0.5～1%, titanium dioxide 3～7%.
A kind of method for preparing the adding calcium fly ash micropore glass carrier of above-mentioned being used for fixing enzyme, choose the polyurethane foam material that porosity is 70-85%, being placed on concentration is in 10～20% sodium hydroxide solutions, under 40～60 ℃ of temperature, soaked 1～3 hour, rub and use the clear water rinsing repeatedly, seasoning behind the removal alkaline solution; With weight percent is adding calcium fly ash 55～75%, binding agent 2～11%, water 10～25% is hybridly prepared into slip, add nanometer titanium dioxide titanium valve or nanometer titanium dioxide zirconium powder 5～20% then, repeatedly several times with exsiccant polyurethane foam dipping slip, under 100～200 ℃ of temperature dry at least 12 hours, make the sintered glass base substrate that contains nano titanium oxide, this sintered glass base substrate is heat-treated, burn the polyurethane foam template, insulation is 60～90 minutes when being heated to 1200 ℃～1400 ℃ of glass sintering temperature then, furnace cooling promptly makes and has the porous glass matrix that highly is communicated with pore.
The present invention also can realize by following measure: binding agent is silicate or silicon dioxide colloid.
The present invention the industrial residue adding calcium fly ash with power plant be main raw material make have in the micropore glass that highly is communicated with pore the nanometer titanium dioxide of an adding titanium valve, adopt the chelating method, utilize sequestering action enzyme directly to be chelated on the sintered glass that contains nano titanium oxide, enzyme combines with carrier firmly, enzyme active higher, have high handling stability, thus the above-mentioned shortcoming that exists when having overcome sintered glass as fixed enzyme vector.
Embodiment
The invention will be further described below in conjunction with embodiment:
Embodiment 1: the polyurethane foam of choosing porosity and be 70-85% is processed into the sphere that diameter is 2mm-4mm, being placed on concentration is in the 10--20% sodium hydroxide solution, soak 1-3h down at 40-60 ℃, rub and use the clear water rinsing repeatedly, seasoning behind the removal alkaline solution; With weight percent is that adding calcium fly ash 65%, silicon dioxide colloid 7%, water 18% are hybridly prepared into slip, add nanometer titanium dioxide titanium valve 10%, repeatedly several times with exsiccant polyurethane foam dipping slip, dry at least 12h under 100-200 ℃ makes the sintered glass base substrate that contains nano titanium oxide.This sintered glass base substrate is heat-treated, burn the polyurethane foam template, when being heated to 1200 ℃-1400 ℃ of glass sintering temperature then about insulation 60-90min, furnace cooling, promptly make and have the spherical porous granulated glass sphere that highly is communicated with pore, its diameter is 1.2mm-3mm.The weight of present embodiment adding calcium fly ash ingredient requires: calcium oxide 29%, aluminium sesquioxide 13%, silicon-dioxide 49%, ferric oxide 2%, manganese oxide 1%, titanium dioxide powder 6%.
The present embodiment silicon dioxide colloid also can adopt silicate as binding agent, and the nanometer titanium dioxide titanium valve also can use the titanium dioxide zirconium powder to substitute.
Embodiment 2: the polyurethane foam of choosing porosity and be 70-85% is processed into the rectangle of 6cm * 8cm * 0.8cm, being placed on concentration is in the 10--20% sodium hydroxide solution, soak 2-6h down at 40-60 ℃, rub and use the clear water rinsing repeatedly, seasoning behind the removal alkaline solution; With weight percent is that adding calcium fly ash 55%, silicon dioxide colloid 10%, water 25% are hybridly prepared into slip, add nanometer titanium dioxide titanium valve 10%, repeatedly several times with exsiccant polyurethane foam dipping slip, dry at least 12h under 150-250 ℃ makes the sintered glass base substrate that contains nano titanium oxide.This sintered glass base substrate is heat-treated, burn the polyurethane foam template, when being heated to 1200 ℃-1450 ℃ of glass sintering temperature then about insulation 1-2h, furnace cooling, promptly make and have the rectangle sintered glass sheet that highly is communicated with pore, its specification is 5cm * 7cm * 0.6cm.The weight of present embodiment adding calcium fly ash ingredient requires: calcium oxide 20%, aluminium sesquioxide 16%, silicon-dioxide 53%, ferric oxide 3%, manganese oxide 1%, titanium dioxide 7%.
The present embodiment silicon dioxide colloid also can adopt silicate as binding agent, and the nanometer titanium dioxide titanium valve also can use the titanium dioxide zirconium powder to substitute.
Embodiment 3: the polyurethane foam of choosing porosity and be 70-85% is processed into diameter and is 3cm, highly is the right cylinder of 5cm, being placed on concentration is in the 10--20% sodium hydroxide solution, soak 2-6h down at 40-60 ℃, rub and use the clear water rinsing repeatedly, seasoning behind the removal alkaline solution; With weight percent is that adding calcium fly ash 70%, silicon dioxide colloid 5%, water 10% are hybridly prepared into slip, add nanometer titanium dioxide titanium valve 15%, repeatedly several times with exsiccant polyurethane foam dipping slip, dry at least 12h under 150-250 ℃ makes the sintered glass base substrate that contains nano titanium oxide.This sintered glass base substrate is heat-treated, burn the polyurethane foam template, when being heated to 1200 ℃-1500 ℃ of glass sintering temperature then about insulation 2h, furnace cooling, promptly make and have the columniform sintered glass post that highly is communicated with pore, its specification is that diameter is 2cm, highly is 4.2cm.Calcium oxide 31%, aluminium sesquioxide 14.5%, silicon-dioxide 50%, ferric oxide 1%, manganese oxide 0.5%, titanium dioxide 3%.
The present embodiment silicon dioxide colloid also can adopt silicate as binding agent, and the nanometer titanium dioxide titanium valve also can use the titanium dioxide zirconium powder to substitute.
Immobilized enzyme porous glass matrix provided by the invention, its core are sintered glass.Spherical in shape, the cylindrical or rectangle of this carrier, its surface is tridimensional network, and inside exists the connection pore of a large amount of continuous distribution, except that having the micron order micropore, also has macroscopic millimeter level pore.This porous glass matrix material is that the industrial residue adding calcium fly ash with power plant is that main raw material is made, adding calcium fly ash and adhesive solution are hybridly prepared into slip, add the nanometer titanium dioxide titanium valve more according to a certain percentage, flood slip, drying with polyurethane foam several times repeatedly, make the sintered glass base substrate that contains nano titanium oxide.This sintered glass base substrate is heat-treated, burn the polyurethane foam template, be heated to glass sintering temperature insulation, cooling then, promptly make and have the sintered glass that highly is communicated with pore.This carrier ventilate rate 〉=80%, pore diameter range between 50 μ m-2000 μ m, ultimate compression strength 〉=0.5Mpa, can sterilize, clean and utilize again, has immobilized enzyme effective (transformation period is 40-50 days), immobilized enzyme vigor height (relative enzyme activity 〉=86%, enzymatic activity recovery is 42.6-53%), production cost is relatively low, production technique is simple relatively, and energy-conserving and environment-protective are practical, have wide range of applications, be beneficial to advantages such as suitability for industrialized production.
The present invention also can realize by the listed ratio of following table (weight percent), its preparation method can adopt above-mentioned three embodiment in any one.
| Embodiment | Adding calcium fly ash | Silicate | Water | The nanometer titanium dioxide titanium valve |
| Embodiment 4 | 75 | 2 | 18 | 5 |
| Embodiment 5 | 55 | 11 | 14 | 20 |
| Embodiment 6 | 60 | 8 | 25 | 7 |
Listed embodiment is corresponding with last table, and the ratio of adding calcium fly ash ingredient (weight percent) is:
| Embodiment | Calcium oxide | Aluminium sesquioxide | Silicon-dioxide | Ferric oxide | Manganese oxide | Titanium dioxide |
| Embodiment 4 | 31 | 16 | 42 | 3 | 1 | 7 |
| Embodiment 5 | 30 | 9 | 52 | 2.2 | 0.8 | 6 |
| Embodiment 6 | 28 | 14 | 50 | 2 | 1 | 5 |
Claims (4)
1, a kind of adding calcium fly ash micropore glass carrier of being used for fixing enzyme, adopting adding calcium fly ash, binding agent, water, nanometer titanium dioxide titanium valve is that feedstock production forms, its technical characterictic is that the weight of raw material consists of and contains: adding calcium fly ash 55～75%, binding agent 2～11%, water 10～25%, nanometer titanium dioxide titanium valve or nanometer titanium dioxide zirconium powder 5～20%.
2, a kind of method for preparing the adding calcium fly ash micropore glass carrier of described the being used for fixing enzyme of claim 1, it is characterized in that: choose the polyurethane foam material that porosity is 70-85%, being placed on concentration is in 10～20% sodium hydroxide solutions, under 40～60 ℃ of temperature, soaked 1～3 hour, rub and use the clear water rinsing repeatedly, seasoning behind the removal alkaline solution; With weight percent is adding calcium fly ash 55～75%, binding agent 2.5～10.5%, water 10～25% is hybridly prepared into slip, add nanometer titanium dioxide titanium valve or nanometer titanium dioxide zirconium powder 5～20% then, repeatedly several times with exsiccant polyurethane foam dipping slip, under 100～200 ℃ of temperature dry at least 12 hours, make the sintered glass base substrate that contains nano titanium oxide, this sintered glass base substrate is heat-treated, burn the polyurethane foam template, insulation is 60～90 minutes when being heated to 1200 ℃～1400 ℃ of glass sintering temperature then, furnace cooling promptly makes and has the porous glass matrix that highly is communicated with pore.
3, according to adding calcium fly ash micropore glass carrier of claim 1 or 2 described being used for fixing enzymes and preparation method thereof, it is characterized in that said binding agent is a silicate.
4, according to adding calcium fly ash micropore glass carrier of claim 1 or 2 described being used for fixing enzymes and preparation method thereof, it is characterized in that said binding agent is a silicon dioxide colloid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008101607779A CN101423829A (en) | 2008-11-18 | 2008-11-18 | Adding calcium fly ash micropore glass carrier for immobilized enzyme and preparation method thereof |
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| CNA2008101607779A CN101423829A (en) | 2008-11-18 | 2008-11-18 | Adding calcium fly ash micropore glass carrier for immobilized enzyme and preparation method thereof |
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| CN101423829A true CN101423829A (en) | 2009-05-06 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101914519A (en) * | 2010-07-08 | 2010-12-15 | 东南大学 | Method for preparing hybridizing gel carrier immobilized enzyme |
| CN102876845A (en) * | 2012-06-28 | 2013-01-16 | 辽宁天和科技股份有限公司 | Method for producing ultra-low phosphorus steel through applying pre-melting calcium ferrite to refine outside LF (Ladle Furnace) molten steel furnace |
| CN108516840A (en) * | 2018-04-16 | 2018-09-11 | 柳州市柳晶科技股份有限公司 | A method of preparing porous material using Industry Waste ash |
-
2008
- 2008-11-18 CN CNA2008101607779A patent/CN101423829A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101914519A (en) * | 2010-07-08 | 2010-12-15 | 东南大学 | Method for preparing hybridizing gel carrier immobilized enzyme |
| CN102876845A (en) * | 2012-06-28 | 2013-01-16 | 辽宁天和科技股份有限公司 | Method for producing ultra-low phosphorus steel through applying pre-melting calcium ferrite to refine outside LF (Ladle Furnace) molten steel furnace |
| CN108516840A (en) * | 2018-04-16 | 2018-09-11 | 柳州市柳晶科技股份有限公司 | A method of preparing porous material using Industry Waste ash |
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Open date: 20090506 |